Plasmonic resonances of closely coupled gold nanosphere chains

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Journal Article
Journal of Physical Chemistry C, 2009, 113 (7), pp. 2784 - 2791
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The optical properties of an ordered array of gold nanospheres have been calculated using the T-matrix method in the regime where the near-fields of the particles are strongly coupled. The array consists of a one-dimensional chain of spheres of 15 nm diameter where the number of spheres in the chain and interparticle spacing is varied. Calculations have been performed with chains up to 150 particles in length and with an interparticle spacing between 0.5 and 30 nm. Incident light polarized along the axis of the chain (longitudinal) and perpendicular (transverse) to it are considered, and in the latter case for wavevectors along and perpendicular to the chain axis. For fixed chain length the longitudinal plasmon resonance red shifts, relative to the resonance of an isolated sphere, as the interparticle spacing is reduced. The shift in the plasmon resonance does not appear to follow an exponential dependence upon gap size for these extended arrays of particles. The peak shift is inversely proportional to the distance, a result that is consistent with the van der Waals attraction between two spheres at short range, which also varies as 1/d. The transverse plasmon resonance shifts in the opposite direction as the interparticle gap is reduced; this shift is considerably smaller and approaches 500 nm as the gap tends to zero. Increasing the number of particles in the chain for a fixed gap has a similar effect on the longitudinal and transverse plasmon. In this case, however, the longitudinal plasmon tends toward an asymptotic value with increasing chain length, with the asymptotic value determined by the interparticle spacing. Here, the approach to the asymptote is exponential with a characteristic length of approximately two particles, at small interparticle spacings. This approach to an asymptote as the chain length becomes infinite has been verified in a finite element calculation with periodic boundary conditions. © 2009 American Chemical Society.
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